Cupriferous trisazo-dyestuffs



2,753,315.? Patented July 3, 1956 United States Patent c CUPRIFEROUSTRISAZO-DYESTUFFS with a pyrazolone of the formula Henri Riat,Arlesheim, Switzerland, assignor to Ciba (4) HO I Limited, Basel,witzerland, a Swiss firm No Drawing. Application October 27, 1952, no Ais Serial No. 317,131 01H H03 Claims. o]. 260147) 41 diazotizing theresulting amino-monoazo-dyestufi, and coupling it with a middlecomponent of the formula 15 0-Alk 1 The present lnventron providescuprtferous trisazoy dyestufis which, like the dyestufi of the formulaO-Cu-O 0 On i C-N- OH=CH- -N=N- N=N l USE I E083 E038 Nn oo Hoa 5 H3Hols correspond to the general formula and finally coupling the diazocompound obtained from X Cu 0 ?--Cu-O 1L o N-Oon=oH- N=N-RzN=N-iia1N=N-C I A 03H HO C=N l in which: the resulting amino-disazo-dyestuifwith a suitable end X represents a hydroxyl or carboxylic acid groupoccupycomponent of the formula ing a position vicinal to the azo-linkageand bound in 0H complex union with the copper atom, k,

Y represents a methyl or carboxylic acid group,

R1 represents an aromatic radical of the benzene series, 40

R2 represents a benzene or naphthalene radical bound in para-position tothe azo linkages, and

R3 represents an aromatic radical, and in which the group O--Cu-0 isbound to the radicals R2 and R3 in positions vicinal to the azo linkage.

and advantageously a hydroxynaphthalene capable of coupling inortho-position with respect to the hydroxyl group.

In general it is of advantage to choose initial components whichcontain, in addition to the alkoxy group (advantageously methoxy),carboxylic acid group or hydroxyl group occupying a position vicinal tothe diazotizable amino group, a group imparting solubility, espe ciallya sulfonic acid group.

The following compounds may be mentioned as These cupriferoustrisazo-dyestufis are made in accordance with the invention by treatinga trisazo-dyestutf corresponding to the general formula R1 represents anaromatic radical of the benzene series 4 amln0l;1hydroxybeflzeile'z'ciarboxyhc containing as a substituent inortho-position to the azo l'hydmxy finzene nsu.lfom.c and linkage ahydroxyl, alkoxy or carboxylic acid group, droxybenzene-fbsultonic ac d,Z-ammo-l-hydroxybenzene- R2 represents a benzene or naphthalene radicalbound in acid, Y Y ara.posifion to the azo groups and containing inbenzene-4:6-disulfonic acid, 4 chloro-2-arnino-1-hydr0xyh iti to h N N Rgroup a hydroxyl benzene 6- sulfonic acid, 1-amino-2-methoxybenzene, oralkoxy group, and 1-amino-2-methoxybenzene-S-sulfonic acid, l-aminoben-R3 represents an aromatic radical bound to the azo-linkage zene 2carboxylic acid, l-aminobenzene-Z-carboxylic in a position vicinal tothe hydroxyl group, acid-S-snlfonic acid, 1-aminobenzene-Z-carboxylicacid-4- sulfonic acid, S-ethoxy-l-aminobenzene-Z-carboxylic acid andl-amino-2-carboxymethoxyd-methoxybenzene.

As pyrazolones of the Formula 4 there come into consideration l-[4"-aminostilbene-(4) ]-5-pyrazolone-3-carboxylic acid-2':2-disulfonicacid and especially 1-[4'2 with an agent yielding copper in such mannerthat any ortho-alkoxy-ortho'-hydroxy-azo-groupings are converted intoortho:ortho'-dihydroXy-azo-copper complexes.

The trisazo-dyestufis of the Formula 3 serving as starting materials canbe made by coupling the diazo comami'nostilbene (4')] 3methyl-S-pyrazolone-Z':2"-disulfonic acid of the formula r= CH:

The aminoazo-dyestufis obtainable from the above mentioned initialcomponents and pyrazolones are after converting them into their diazocompounds, coupled with a middle component of the formula HR2NH2, thelatter component containing as a group capable of forming metalcomplexes in ortho-position to the amino group, for example, a hydroxyl,carboxymethoxy, an ethoxy or advantageously a methoxy group. There maybe used middle components of the benzene or naphthalene series such, forexample, as l amino-Z-methoxy-S-methylben- Zene, 1-arnino-2S-dimethoxybenzene, l-amino-2 5-diethoxybenzene,l-amino-2-methoxy-5-ethoxybenzene, 1- arnino-Z-ethoxy-S-methoxybenzene,l-amino-Z-methoxycarboxy-S-methylbenzene orl-arnino-2-hydroxy-5-methylbenzene. Especially valuable dyestffs areobtained from l-amino-2-alkoxynaphthalenes and above all from 1-aminoe2-alkoxynaphthalene-6- or -7-sulfonic acids. As examples there maybe mentioned l-amino-2-methoxynaphthalene, l-amino-2-ethoxynaphthalene,l-amino-2- methoxynaphthalene-6-sulfonic acid,l-amino-Z-methoxynaphthalene-7-sulfonic acid and1-amino-2-ethoxynaphthalene-6- or -7-sulfonic acid.

As end components of the formula there come into consideration arylcompounds capable of coupling in ortho-position relatively to a hydroxylgroup, advantageously those of the naphthalene series such asZ-hydrox'ynaphthalenes, hydroxynaphthalene sulionic acids and especiallyaminohydroxynaphthalene sulfonic acids containing a substituted aminogroup, for example, an arylamino group or acylamino group. As examplesthere may be mentioned; 2-hydroxynaphthalene, 2-hydroxynaphthalene-6-sulfonic acid, l-hydroxynaphthalene-4-sulfo nicacid, l-hydroxynaphthalene-3:6- or -3:8-di sulfonic acid,2-hydroxynaphthalene-3:6-disulfonic acid, 1 :8-dihydroxynaphthalene-36-disulfonic acid, l-amino- 5-hydroxynaphthalene-7-sulfonic acid,l-amino-S-hydroxynaphthalene-4-sulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-8-hydroxynaphthalene6sulfonic acid,Z-amino-6-hydroxynaphthalene-8-sulfonic acid,l-amino-8-hydroxynaphthalene-Z:4- or -3:6- or -4:6-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-3 6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-3:6- disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-4- sulfonic acid,2-acetylamino-6-hydroxynaphthalene-8-sulfonic acid,2-benzoylamino-6hydroxynaphthalene-8-sulfonic acid; nitrogen substituted2-amino-5-hydroxy naphthalene-7-sulfonic acids, such as2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-.benzoylamino-5ahydroxynaphthaleneJ-sulfonic acid,2-.(4chlorobenzoylamino)-5-hydroxynaphthalene-7-sulfonic acid,Z-phenylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-(2- or4-methoxyphenylamino) -5-hydroxynaphthalene-7-sulfon ic acid, 2-(3- or4'-carboxymethoxyphenylamino)-5-hydroxynaphthalene-7-sulfonic acid,2-(4-methylphenylamino) -5-hydroxynaphthalene-7 3'-disulfonic acid,2-.(4- chlorophenylamino) -5-hydroxynaphthalene-7 3 -disulfonic acid,Z-phenylamirio-5 hydroXynaphthalene-7:3- or 7 4'-disulfonic acid.

The dyestuffs of the Formula 3 can be made by the usual known methods.The coupling of the initial component with the pyrazolone isadvantageously carried out in a weakly alkaline medium, and couplingwith the middle component in a weakly acid to neutral medium, while 4the final coupling is advantageously carried out in the presence ofpyridine.

In order that the cupriferous dyestuffs obtained by the present processshall be suificiently soluble it is generally necessary so to choose thecomponents used for synthesizing the initial dyestuffs of the generalFormula 3, that the dyestuffs contain at least four and advantageously4-6 sulfonic acid groups.

The treatment with an agent yielding copper is carried out in suchmanner that the cupriferous dyestuffs of the Formula 2 are obtained fromthe dyestuffs of the Formula 3 with the conversion of anyortho-alkoxy-orthohydroxyazo-groupings intoortho:ortho'-dihydroxyazocopper complexes, that is to say, in suchmanner that two atoms of copper are bound in complex union for eachmolecule of disazo dyestuff accompanied by dealkylation of the alkoxygroups taking part in the formation of the complex. As is known thisreaction takes place more easily withortho:ortho-dihydroxy-azo-groupings than withortho-hydroxy-ortho-alkoxy-azo-groupings, so that in the latter case alonger duration of treatment and/or a treatment at a higher temperatureis indicated. The coppering may be carried out, for example, with saltsof divalent copper in a weakly acid aqueous medium. However, thedyestuffs can also be coppered by the known process in which thecoppering is carried out advantageously for several hours in thevicinity of C. in an aqueous medium with the use of a copper tetramminecomplex in the presence or absence of an excess of amine or ammonia. Ofspecial advantage in some cases of this kind is the process which iscarried out in the presence of an hydroxyalkylamine, especiallyethanolamine or a copper complex derived therefrom.

Dyestuffs of the general Formula 3, of which the radical R2 represents anaphthalene radical containing an alkoxy group in a position vicinal tothe azo linkage connecting R2 and R3, for example, dyestuffs in whichthe radical R2 corresponds to the formula O-OH3 (01 (I)-C7H5) H0 8 arein general coppered with advantage by means of copper sulfate with theaddition of an alkali acetate.

On the other hand it has been found that in the case of those dyestuffswhich contain at the aforesaid position in the molecule analkoxy-benzene radical, for example, one of the formulae the conversioninto the ortho:orthd-dihydroxy-copper complex is advantageously carriedout with the use of copper tetrammine sulfates.

The cupriferous dyestuffs obtainable by the process of the invention arenew and correspond to the above Formula 2. I This formula undoubtedlygives the correct stoichiometric quantities of copper and the correctpositions ofthe copper atoms in the complex, but the distri greasesbution of the main and secondary valences in the complex union of thecopper has not been established with certainty.

The new cupriferous dyestuffs of the Formula 2 can be used for dyeing orprinting a very wide variety of materials such as wool, silk andespecially cellulose fibers, such as cotton, linen and also artificialsilk and staple fibers of regenerated cellulose. In general grey toolivegreen dyeings of good fastness to light are obtained, which alsowithstand an ordinary anti-creasing treatment, for example, by means ofurea-formaldehyde artificial resins.

The following examples illustrate the invention, the parts andpercentages being by weight:

Example 1 21.7 parts of 1-aminobenzene-2-carboxylic acid-4-sulfonic acidare dissolved in 150 parts of water with 11 parts of anhydrous sodiumcarbonate, then acidified with 25 parts of hydrochloric acid of 30 percent. strength, and diazotized at -l0 C. with 6.9 parts of sodiumnitrite dissolved in 50 parts of water. The diaZo-compound is coupledwith 43 part of 1-[4"-aminostilbene- (4')]-3-methyl-5-pyrazolone2':2"-disulfonic acid in a solution rendered alkaline with sodiumbicarbonate. The excess of sodium bicarbonate is neutralized withhydrochloric acid, the solution is mixed with 6.9 parts of sodiumnitrite, and the monoazo-dyestuif is diazotized by pouring in 40 partsof hydrochloric acid of 30 per cent. strength. After stirring for 2-3hours at room temperature the mixture is neutralized with sodiumacetate, and coupled with 25.3 parts ofl-amino-Z-methoxynaphthalene-6-sulfonic acid dissolved in the form ofits sodium salt with parts of sodium acetate in 200 parts of water. Bygradually adding 40 parts of sodium carbonate solution of 10 per cent.strength the coupling S 0 311 g H 0 38- is accelerated. When thecoupling is finished, the com pling mixture is rendered alkaline withsodium carbonate, and the disazo-dyestufi is salted out and filteredofi. The dyestuif paste is dissolved in 1500 parts of water with theaddition of sodium hydroxide solution, then mixed with 7 parts of sodiumnitrite, and diazotized by pouring in 40 parts of hydrochloric acid of30 per cent. strength. The whole is stirred for about 1 hour at roomtemperature, and the diazo compound, after being filtered oil andstirred in 1500 parts of ice water, is introduced into a solution,cooled to 5 C., of 28 parts of2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 25 parts of sodiumbicarbonate and 150 parts of pyridine in 200 parts of water. When thecoupling has finished, the disaZo-dyestuff of the formula O--Cu-O NH-oO-GH: HOz S is salted out, filtered oil, and boiled in parts ofcrystalline copper sulfate and 40 parts of sodium acetate in 3000 partsof water for 10 hours under reflux, in order to form the copper complex.The copper complex is then salted out, filtered oil, and converted inthe usual manner into its sodium salt. When dry, the dyestuif is a darkpowder which dissolves in water with an olivegreen coloration, and dyescotton olive-green tints which are fast to light.

In the following table are given a number of further valuabletrisazo-dyestuffs, which are made by coupling in the manner described inthis example the diazo compounds given in column I With1-[4"-aminostilbene- (4')]-3-methyl-S-pyrazolone-Z:2-disulfonic acid,diazotizing again, and coupling with the middle components given incolumn II, again diazotizing the aminodisazo-dyestuifs so obtained andcoupling with the end components given in column III, and converting thetrisazo dyestuifs into their complex copper compounds.

I II III IV Tint oi dyeing Initial component Middle component Endcomponent of the complex compound on cotton 11-aminobenzene-2-carl-amiuo-Z-methoxy- 2-benz0ylamino-5-l1yolive-green.

boxylic acidA-sulnaphthalene-fi-suldroxynaphthaleneionic acid. ionicacid. 7-sulionic acid. 2 -do do 1-acety1an1ino-8-hyolive.

droxynaphthalene- 4-su1ionic acid. 3 ..d0 ..do l-benzoylamino-i-hy- D0,

droxynaphthalene- 4-sul1onic acid. 4 do .do 2-benzoylan1ino-6-hy- Do.

droxynaphthalene- B-sulfonie acid. 5 -do ..do Z-acetylamino-fi-hy- Do.

droxynaphthalene- 8-sulf0nlc acid. 6 do do 2-phenylamino-8-hy- Do.

droxynaphthalenefi-suliom'c acid-3- carboxylic acid. 7 do .doZ-hydroxynaphthagreenoiive.

lene-B-sultonic acid. 8 do ..do 1-hydroxynaphthaolive.

lenel-sulfonic acid. 9 do do 2-lliydroxynaphthagreen-olive.

ene. 10 do 1-amino-2-methoxy- Z-acetyIamino-S-hy' yellowish green.

naphthalene. droxynaphthalene- 7-su1fonic acid. 11 .dol-amino-Z-ethoxydo olive-green.

naphthalcne'fi-sultonic acid. 12 l-aminobenzene-Z-carl-amino-2-methoxy-Z-acetylamino-fi-hy D0. boxylic acid-5-su1-naphthalene-fi-suldroxynaphthaleneionic acid. Ionic acid. 7-suliouicacid. 13 l-aminobcnzene-2-cardo .-do green-olive.

boxylic acid. 14 l-aminobenzene- -carl-amino-Z-methoxy- .do olive green.

boxylic acid-et-sulnaphtha1ene-7-suiionic acid. tonic acid.

7 8 Dyestuff No. 3 of the above table corresponds to the sodiumhydroxide solution, then mixed with 6.9 parts formula of sodium nitriteand diazotization is brought about by CH3 H038 SOQH Example 2 pouring in40 parts of hydrochloric acid of 30 per cent.

h di a dy tufl (Lamimbenzene 2 carboxylic strength at 15 -20 The wholeis stirred for about 2 id 4 511501110 id- 1 4" i ilb (4')]- hours,neutralized with sodium bicarbonate until Congo 3 methyl 5 pyrazolone2'z2 di ulfoni aeidpaper gives a violet coloration, and the diazocompound l-amino-Z-methoxynaphthaleuc-G-sulfonic acid) obtained 15 iWlth a neutral solutlon f Parts of as described in Example 1 isdiazotized. The diazo comamlnojzdneihoxynaphthalene'6'sulfonlc mild andParts pound is filtered ofi, stirred in' ice water and coupled in GISPdWm acetate 111 Parts of W y gradually the presence of 30 parts ofsodium bicarbonate and 100 addmg 9 of Sodlum Carbonate 111 50 P i ofWater parts of pyridine with 40 parts of 2-(4-methylphenyl 20 thecoupling is brought to amend. The coupling mixtureamino)-S-hydroxynaphthaleue 7:3-disulfonic acid in 300 18 renderedalkaline W1th S d u hyclloXldfi Solution, and parts of water. Thetrisazo-dyestuft' so formed is salted thB dlsaZo-dyestllfi Saltedv u andfiltered ofi. The out, filtered off and converted into its coppercomplex dyestllfl Paste 15 dlSsOll/ed 1500 Parts of Water, if

by heating it at the boil under reflux for 6 hours with 50 s d ith theaddition ot a small amount of sodium parts of crystalline coppersulfate, 100 parts of ammonia hydroxide solution, then mixed with 7parts of sodium l ti f 25 per t, trcngth d 2.0 parts f th op nitrite and200 parts of sodium chloride, and diazotized amine in 2000 parts ofwater. The copper complex, after by pouring in 40 parts of hydrochloricacid of per being worked up, in a dark powder which dissolves in nrength- The WhOle is stirred at l5-20 C., water with a green colorationand dyes cotton yellowish filtered off, the diazo compound is stirred in1500 parts green tints which are fast to light. 30 of ice water, and theresulting suspension is introduced By using, instead of2-(4'methyl)-phenylamino-5- into an ice-cold solution of parts ofZ-benzoylaminohydroxynaphthalene-7:3-disulfonic acid, 2-phenylamino-5-hydroxy-naphthalene-7-sulfonic acid, 30 parts of sodi-5-hydroxynaphtbalene-7-sulfonic acid or 2-(4'-carboxyum carbonate, 150parts of pyridine and 200 parts ofmethoxyphenylamino)-5-hydroxynaphthalene7 sulfonic Water. When thecoupling is finished, the trisazo-dyestuff acid there are obtaineddyestuffs having similar properof the formula O-Cu-O 0 Cu 0 I I I CH;110 8 ties. The trisazo dyestuff obtained this way with 2- u is saltedout, filtered off and boiled under reflux for 10phenylamino-S-hydroxy-naphthalene-7 sulfonic acid corhours in 4000 partsof water with parts of crystalline responds to the formula coppersulfate in the presence of 40 parts of sodium CH3 H035 Instead of theabove mentioned disazo-dyestuff, there acetate. The resulting complexcopper compound is then may be used the corresponding diaZo-dyestufi"from salted out with sodium chloride, filtered 01?, and con- 1 [4"aminostilbene (4')] 5 pyrazolone 3 carverted into its sodium salt inknown manner. The dyeboxylic acid-2':2-disulfonic acid. stuff when dryis a dark powder and dyes cotton olive By using, instead of2-(4'-methylphcnylamino)-5-hytints. droxynaphthalcne-7:3-disulfonicacid, 2-phenylamino-8- By using in this example, instead of theZ-benzoylhydroxynaphthalene-6:3'-disulfonic acid orZ-Phenylamiamino-5-hydr0xynaphthalene-7-sulfonic acid, a correno 8hydroxynaphthalene 6 sulfonic acid 3' carsponding quantity ofZ-acetylamino-S-hydroxynaphthaboxylic acid, there are obtainedcupriferous dyestuffs lene-7-sulfonic acid a similar dyestu'lf isobtained. which dye cotton olive tints. Example 4 Example 3 The diazocompound from l8.9 parts of Z-amino-l- 20.3 parts ofZ-amino-1-methoxybenzene-4-sulfonic hydroxybenzene-4-sulfonic acid iscoupled in a solution acid are diazotized in the usual manner, and thediazo rendered alkaline with sodium carbonate with 43 parts of compoundis introduced into a solution, rendered alkaline l [4 aminostilbcne (4)]3 methyl 5 pyrazwith sodium carbonate, of 43 parts of 1-.[ 4-amino-0lone-2:2-disulfonic acid, the monoazo-dyestuif is distilbene (4')] 3methyl 5 pyrazolone 2'22 diazotized as described in Example 3 then mixedwith 40 sulfonic acid. When the coupling is finished, the excess partsof sodium acetate, and coupled with 13.7 parts of of sodium carbonate isneutralized with hydrochloric acid, l-aminO-Z-methoXy-S-methylbenzene,dissolved in the partially precipitated monoazo-dyestuff is again partsof water and 11 parts of hydrochloric acid of 30 per brought intosolution by means of a small amount of .5 cent strength. Thedisazodyestuff is separated, if desired,

,9 w purified by reprecipitation, dissolved in 2000 parts of dyestutfwhich dyes cotton somewhat more yellowish olive water having a weaklyalkaline reaction, mixed with 7.2 tints.

parts of sodium nitrite, and diazotized by pouring in 40 By using inthis example, instead of 1 [4 aminostilparts of hydrochloric acid of 30per cent. strength. The bene (4')] 3 methyl pyrazolone 2'22" disul-Whole is stirred for 1-2 hours at 20 C., coupled with 35 5 fonic acid, 1[4 aminostilbene (4')] 5 pyrazoloneparts of2-benzoylamino-5-hydroxynaphthalene7-sulfonic 3 carboxylic acid 2':2"disulfonic acid there is obacid in a solution rendered alkaline withsodium cartained at dyestulf having similar properties.

bonate, in the presence of 40 parts of pyridine. The resultingtrisazo-dyestufi is filtered, oil. In order to convert Example 6 thedyestutf into its copper complex, the dyestutf paste 10 100 parts ofcotton are entered at 40 C. into a dyeis dissolved in 3000 parts of hotwater with the addition bath which contains in 3000 parts of water 1part of the of 40 parts of ethanolamine. The solution is mixed withdyestuff obtainable as described in the first paragraph of an ammoniacalsolution of copper sulfate (corresponding Example 1. The dyeing iscarried on for /2 hour while to 50 parts of CuSO4.5H20) and heated at 95C. for increasing the temperature to 90 C., 30 parts of crystal- 8-l0hours. The resulting copper complex is then preline sodium sulfate areadded, and dyeing is continued for cipitated by means of sodiumchloride, filtered oif and a further /2 hour at 90-95 C. The cotton isthen rinsed dried. There is obtained a blackish powder which disanddried. There is obtained an olive green dyeing of solves in warm waterwith an olive-grey coloration and very good fastness to light. dyescotton grey tints. What is claimed is:

By using in this example, instead of the Z-benzoylamino- 1. Acupriferous tn'sazo-dyestuff of the formula X---Cu 0 OCu--O ti)-N-OH=OH- N=.N-itz-N=N-l h Rl N=NC I g 5-hydroxynaphthalene-7-sulfonicacid, the corresponding in which X represents a member selected from thegroup quantity of 2 acetylamino 5 hydroxynaphthalene-7- consisting of ahydroxyl group and a carboxylic acid sulfonic acid a dyestuff havingsimilar properties is obgroup, said group occupying a position vicinalto the azo r i d, linkage and bound in complex union with the copper Byusing as initial component, instead of Z-amino-latom, Y represents amember selected from the group hydroxybenZene-4-sulfonic acid,2-amino-1-hydroxybenconsisting of a methyl and a carboxylic acid group,R1 zene-4-sulfonic acid-6-carboxylic acid there is obtained a representsan aromatic radical of the benzene series, R2 dyestuff which correspondsto the formula represents a member selected from the group consisting 0Cu 0 0 Cu 0 HOOC NN O\ l sons Both H30 H085 NHOC- and which also dyescotton grey tints. of a benzene and a naphthalene radical bound in para-Exam le 5 position to the azo-linkages and R3 represents an aromaticradical of the naphthalene series, the group The diazo compound, whichhas been obtained by diazotizing the monoazo-dyestutl of Example 1 from21.7 --O- parts of l aminobenzene 2 carboxylic acid 4 sulionic acid and43 partsof 1 aminqstilbene being bound to the radicals R2 and R3 inpositions vicinal 3-methyl-5-pyrazolone-2':2"-disulfonic acid, iscoupled in to the azo linkage. the presence of sodium acetate withl-amino-Z-methoxy- 2. A cupriferous trisazo-dyestuff of the formulaS-methylbenzene, and the resulting disazo-dye'stutf is sep- 5 in "whichthe COO-group stands in ortho-position to r if desired, Purified y pfi pl diazotized the azo linkage, R1 represents an aromatic radical of thegag ii g i ti s ii gigiigg g 5 1;2 3:2 3 28 benzene series, R2represents a naphthalene radical bound parts of py with 35 parts ofbenzoylaml-no in paraposition to the azo-linkages and R3 represents anhydroxynaphthalene 7 sulfonic acid. The trisazo-dyeradical of thenaphthalene Series, the group stuff is isolated and converted by themethod of Example" 4 into its copper complex which dyes cotton olivetints. -O-Cu-O- By using in this example, instead of 1 amino 2- I imethoxy 5 methylbenzene, a corresponding quantity of betng bound to theradicals R2 and Rs in positions vicinal .1 amino 2:5 dimethoxybenzene,there is obtained a to the azo linkage,

3. A cupriferous trisazo-dyestuff of the formula 12 in which the'-COOgroup stands in ortho-position to in which the -OCuO- group boundto R1 stands 10 the azo-linkage, "R1 represents an aromatic radical ofthe in orthoposition to the azo linkage, R1 represents an aromaticradical of the benzene series, R2 represents a naphthalene radical boundin para-position to the azo linkages and Rs representsan aromaticradical of the naphthalene series, the group -O-CuO- being bound to theradicals R2 and R3 in positions vicinal to the azo linkage.

benzene series and R3 represents an aromatic radical of the naphthaleneseries containing a substituted amino group and at least one 'sulfonicacid group and being bound to the 'O-Cu-Ogroup in ortho-position to 15the azo linkage, 'thesulfonic acid group in the naphthalene 4. Acupriferous trisazo-dyestuff of the formula in which the COOgroup standsin ortho-position to the azo-linkage, R1 represents an aromatic radicalof the benzene series and R3 represents an aromatic radical of thenaphthalene series bound to the OCuO-group in ortho-position to the azolinkage, the sulfonic acid group in the naphthalene nucleus I occupyinga p-position. 40

5. A cupriferous trisazo-dyestufl of the formula in which the OCuO-groupbound to R1 stands in SOgH in which the OCu'O--group bound to R1 standsin ortho-position to the azo-linkage, R1 represents an aromatic radicalof the benzene series and R3 represents an aromatic radical of thenaphthalene series bound to the O-Cu--O-group in orthoposition to theazo linkage, the sulfonic acid group in the naphthalene nucleus Ioocupying a ii-position.

6. A cupriferous tn'sazo-dyestufif of the formula l H 0 3S -8.cupriferous trisazo-dyestu'ff of the formula in which the --COOgroupstands in ortho-position to 65 the azo linkage, Rrrepresentsan aromaticradical of the benzene series'and Z represents a substituted aminogroup.

SQIH

t i 9353,5391 u 13 14 9. A cupriferous trisazo-dyestuff of the formulain which the -O-Cu0group bound to R1 stands in 10 ortho-position to theazo linkage, R1 represents an aromatic radical of the benzene series andZ represents a substituted amino group.

10. A cupriferous trisazo dyestutf of the formula SOIH Z C=N in whichthe -OCu-O-group bound to R1 stands in ortho-position to the azolinkage, the -OCu--Ogroup bound to R2 stands in ortho-position to theazo linkage connecting R2 with the naphthalene nucleus, R1 represents anaromatic radical of the benzene series and R2 represents 30 a benzeneradical bound in para-position to the azo linkages.

11. The cupriferous trisazo dyestufi of the formula 12. The cupriferoustrisazo dyestutf of the formula HOaS- I 13. The cupriferous trisazodyestuff of the formula HI HOtS 14. The cupriferous trisazo dyestulf ofthe formula OCl1-O AH HO '15. The cupriferous trisazb dyestufi? of theformula References Cited in the file of this patent UNITED STATESPATENTS 2,277,544 Fischer et a1. Mar. 24, 1-942 2,399,447 Moser Apr. 30,1946

1. A CUPRIFEROUS TRISAZO-DYESTUFF OF THE FORMULA